Indigoid dyestuffs and process of making same



Patented Mar. '29, 1932 monies-n 'roBLE ,0151 Pr sm, SWITZERLAN QASSIGNQREQ FIRM; soom'ry o'FcHEM-I: H

GAL,rlw nustiua-v'ecu BASLE, E; rnnsnn' swmzEnLeun1: a :L dmizie DI I Y HF I Fades "lineman-ems No Drawing. Application-filed January 23, 1930, seri l ze. aaeiflaii ti:iliswitzerlaad Icbruary 2,1929; a

' W-ith aromatic nitroso compounds; such as, for instance;'. 3pfnitroso dimethylaniline "or rythionaphthene.

The present invention relates to new indigoid dyestuffs which are valuable for the production of fast tintskf'lt comprises the process of making the nevv dyestuffs,the dye: f i- Q stuffs themselves, and the material'dyed with he new dyestuffs. I i altihasflzbeen found that new indigoid dyetufisinay be:obtained,as follovvsz'i 111* afirst step chloroacidyl-o-toluidine is transformed into dichloroacidyl o-tolui dine (OH zNHacidyl v:C1;-C1=1:2:4:5) by treating chloro-acidyl 'o -toluidine with chlorinaiting agents,such 'aschlorine or sulfuryl ch oridef In a second step the said dichloro acidybotoluidine' is converted into dichloro-o-toluiis converted into the 2-methyl-4: 5-dich1orophenyl-thioglycollic acid by: condensation with a mono-halo'gen-acetic acid.

In a sixthfstepthe'product thus formedis condensed pby meansof condensing agents, l sucha s chlorosulfonic acid or chlorosulfonic acid and dehydrated'horic acid, to' the corresponding 4:: 5-dichloro-7 -methy1 3*-hfvdroX- In a seventh I p methyle3 hgydronythionaphthene is treated p-nit sophenol, to for-man anil of the 4 =15 diehloi-o#anethylthionaphthenequinonefi 1&3. i In an eighth step the producti obtained by as the" 4 ;5-dmh10r0fl [in concentrated sulfurie acid to, form violet th 2. process of the sixth and seventh f step,

Wh sk he? f n ral for l v wherein m. stands-fora reactive;group-, such 5 as anrl orqQI-I, s-condensedwlth compounds 7 of -he gene e zi m a acenttoeach other, atthe sametirne appertain to an aromatic ring;system,Z and of which therthirdis-NH,S 01' GI Such compounds are "for instance jfiVQ- wherein y represents-a reactive group,such

sentatcm'sjof jvvhioh tW'o areha'rbon atoms inembered condensed ring systems a's for ex m l j-i e ne 'e l xy 's, thi mph hen qu nonesj-2 :3, Ihydr'oxythionaphthenes,. naphtho andthe like, their homologues and'substitu t1on products, anils and halides.

hydroxythiop heries, acenaphthenequinonesfi,

This reaction takes place by heating the components in a solvent which may act as condensing agent.

The dyestuffs thus oh-tained mayfurther v be converted into dyestuffs, containing more halogen by; subsequent i halogenation i l hey correspond vvith thegeneralfo'rinuhQ "i V VI 1 wherein, 9", m and n havethe signification as has hereinbefo-re define'di f Theyfo-ririli'edito violet and Bordeaux poi/vders;vvhich -dissolve to greenish-blueand green'solutions, yielding with hydrosulfite*arid caustic soda solution 7? orange-brown to orange, yellow and. olive vats from Whichcotton is' dyed' fast made in known manner by acidylating chloro-o-toluidine (CH NH Cl =1 2 :4) with acetic anhydride are dissolved in 920 parts of acetic acid of per cent. strength. After addition of parts of sodium acetate 7 5 parts of chlorine areallowed to flow into the solution within 3 hours while stirring at 80-90 C. Stirring is continued for some hours at the same temperature, whereupon the reaction mixture is diluted with 5000 parts of water, filtered, washed free of acid, followed by. drying the dichlo-r-acetyl-otoluidine (CI-I NH-CO-Cl: Ol=1 2: 4: 5) obtained. From alcohol it crystallizes in colorless crystals which melt at 17 0-17 1 C.

218 parts of the dichloroacetyl-o-toluidine thus obtained are dissolved in 2000 parts of alcohol, adding 400 parts 'o-f'caustic alkali, whereupon the whole is boiled for 3 to 5 hours while stirring. After the alcohol has been distilled off, the whole is distilled with steam and the dichlor-o-toluidine r r i 1 v is saponified by heating it in a reflux apparatus with 250 parts of caustic soda solution of 40 B. and 600 parts of alcohol, and in the same solution the product is condensed with 140 partsof chloroacetic acid, dissolved in 168 parts of caustic soda solution of 40 B6. and water. The alcohol is distilled and the residue allowed to cool and acidified with hydrochloric acid. The 2-methyl-4 5-dichloro-phenyl-thioglycollic acid corresponding with the formula 0 a CH:

It is a colorless powder which crystallizes from dilute alcohol in colorless needles, melting at 173 C. By condensation with pnitrosodimethylanili'ne" it can be transformed in known manner into the p-dimethylaminoanil of the 4:5-diohloro-7-methylthionaphthenequinone-2: 3.

Eztample 2 i 216 parts of 5 7-dichlorisatin are converted into the 5:7-dichlorisatin-a chloride by heating them for an hour at 100110 C. with 2500 parts of chlorobenzene and 206.5 parts of phosphorus pentachloride. After the mass has cooled to 80 C. there is run in while stirring, a solution of 233 parts of 4: 5- dichloro-7rmethyl-3-hydroxythionaphthene in 2000 parts of chlorobenzeneQ After a short time the formation of dyestufi' is finished. 7 The dyestuff is filtered and washed with benzene, whereby it is obtained in the form ofa violet powder having the following formula It dissolves in concentrated sulfuric. acid to form a greenish blue solution. With hydrosulfite and caustic soda solution it yields an orange vat, in which the fiber is'dyed very fast violet tints.

Example 3 233 parts of 4: 5-dichloro-7-methyl-3-hydroxythionaphthene and 182 partsof acenaphthene-quinone-8 are suspended in 1800 parts of glacialacetic acid and after addition of 10'parts of concentrated hydrochloric acid the suspensionis heated to boiling, while After filtration the testers stirring, After. a, shorttime -the .,condensation l-i's. .c'omplete tlrie, dyestufiofithe torn u e. 1 I

- 1 pm; N

a green solution. It-yields an -orangebrown vat andi'd-yes oottonred-t-ints ofwery good o fastness.

The same dyestufi? is ng the sprdimethyla inoan lz 0ithe; Li: :5 chloro methylthionaphthenequinon. is: with .acenaphtherione: e e

I, Example 1, I

362 parts of the'dyestuff from 4 :5 dichloro- '7 'metliyl 3=hydroxythionaphthene and -is atinaanilide: of the Lforinula S NH C C 7 ll ll O V 0 C1 are introduced at0 5 G. into a mixture of 192'parts of bromine and 6000 parts of sulfuric acid of 97 per cent, strength. After some stirring the whole is heated in the course of ,12 hours to C. and allowed to remain for a further 12 hours at 4550 C. I At the". end ofthis time the bromination is complete,

the sulfuric acid solution is poured upon ice and the dyestufi which'separates is filtered,

washed and dried. It is a violet powder, sol uble'in concentrated sulfuric acid to form a greenish-blue solution. The'dyestufi' forms an orange vat and dyes cotton violet tints of very good fastness.

amples of dyestufl's obtainable from 4: 5-dichloro-7 methyl-3-hydroxythionaphthene in v accordance with'the invention:

obtained by condens- 1. As a step in the manufacture of new indigoid dyestuiis the herein described p ro- Jduction of'adichloroacetylmetoluidine "which Qconsists. in iheatingi ehloroacetyl-o to- The dyestufif III eorresponds -vyith'the 7 with chlorinatingiagents.; II I '2. As.-a step. -inl the manufactureof new in- A digoidadyestufis theliereinidescribed prdductioniofthetdichloroacetyli-o+toluidine I I H H:QQFG L -0 chlorine; V 1

digoid dyestuffs the hereinzdescribed produc-' tion of the dichloro-o-tolu idine toluidine The following table comprises furtherexwith r n ji eaa atsg 14a; :Aisa step in the nian V digoid dyestufisithjherein steepness 4:5-dichloro-7- f v methylHS-hy- Color of the 3 8; Color of ggg g (Gi 1 .31 V 5O droxythionaphdyestuff the vat cottyn V r V l, V V i. g i

-li 41011818 1 fih e-tlng, v fillqhl reeeetylzo- I v I toluidln 'ei 1 I V I. a isatin-ani- Violet Violet Orange Red-violet LI lide s H: H- -CH :ClzC =1: II. fizzI -dibromisa- Bordeaux Violet Olive Bordeaux l 3 N 3 1 2 I III; I I I III. p dimeth yI Violet Blue-green Orange Violet I I I T: j I I areas: "P ="f" llifiql fi t paphthli o herein described new indigo d dyestufl'sof-tlie 521 2 general formula v I IV. p dimethyl Red Green Yellow Bluish-red OH aminoanil of I r I 3 gllliionagh- 1 enequml v 1,

.. one-2:3 I I S r-=- n I V. p dimeth yl Bluish-red Green Yellow Blush-red I I gmiilloamlpf I I 11- C\ -c oroi metiilyilthio- I I II b I nap enel V I I quimm213 i .2 I v 1'; 5' t I I vwithe e 1 ,2? n- -an ms ands etoms Qf-Avch W I 7 .h I.J.J .'n

3. As a step in the manufacture-of new in V ectur r 1 I 1 105 which consists, in heating,'dichloroacetyl owherein r, n and m stand for atoms of which two are carbon atoms adjacent to each other, which at the same time appertain to an aromatic ring system of the benzene series, and of which the third is NH, S or C, which'products from red to violet and Bordeaux powders which dissolvein vconcentrated sulfuric acid to form violet, greenish-blue, and green solutions, yielding with hydrosulfite and caustic soda solution orange-brown, orange, yellow and olive vats from which cotton is dyed fast red to violet and Bordeaux tints.

7. As new products of manufacture, the

herein described new indigoid dyestuffs of the general formula v CH3 wherein? represents NH or S, and the two carbon atoms C and C appertain to an deaux' to violet powders, which dissolve in concentrated sulfuric acid to form violet and greenish-blue solutions, yielding with hydro sulfite and caustic soda solution olive and orange vatsfrom which cotton is dyed fast red to red-violet and Bordeaux tints.

9. As a new product of manufacture, the herein described new indigoid dyestuff of the formula which forms a violet powder, dissolving in concentrated sulfuric acid to agreenish-blue solution, yielding with hydrosulfite and caustic soda solution an orange vat from which 7 cotton is dyed fast violet tints. I

In witness whereof I have hereunto signed my name this 13th day of January, 1930.

'RIGHARD TOBLER.

aromatic ring system of the benzene series,

whic'h products form red to violet and Bordeaux powders which dissolve in concentrated V sulfuric acid to form violet, greenish-blue, and green solutions, yielding'with hydrosulfite and caustic soda solution orange-brown,

orange, yellow and olive vats from which cotton is dyed fast red to violet and Bordeaux tints.

8. As new products of manufacture, the herein described indigoid dyestuffs of. the general formula v wherein the two carbon atoms G and C apit pertain to an aromatic ring system of the benzene series," which products form Bor- 

